JP3477755B2 - Vinyl chloride resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition used as a sealant for various industries including the automobile industry or a paint for undercoating.

[0002]

2. Description of the Related Art Various industrial products such as automobiles are generally subjected to a pretreatment of undercoating for protection of the sealing base material and final finishing before coating. This undercoat is indispensable on the painted surface of automobiles. A vinyl chloride-based plastisol composition is a typical undercoating material used for this undercoating, but in reality, they are used without being sufficiently satisfied in terms of adhesiveness and stability. is there.

Originally, the main purpose of this undercoating material is to protect the base material against the impact of stones, sand, and other foreign matter, that is, chipping resistance, but in recent years, it has been possible to save energy, save resources and protect the global environment. From a standpoint, even in automobile manufacturing, there is a demand for further weight reduction of the vehicle body, and there is a demand for a thinner coating film thickness. Adhesion to the painted surface is required more than ever before.

Therefore, many vinyl chloride resin compositions for improving the adhesiveness have already been proposed.
JP-A-62-190267, JP-A-62-14858
3, JP-A-59-131669, JP-A-62-4127
8. Japanese Patent Publication No. 59-52901, Japanese Patent Publication No. 2-20659 and the like, a method of adding a urethane prepolymer using an oxime as a blocking agent and an active amino group-containing mono- or polyamide compound to a vinyl chloride resin composition, and an oxime. , Vinyl chloride resin compositions using a urethane prepolymer having lactam, alkylphenol, or oxybenzoic acid ester as a blocking agent.

However, in these known methods, (a) those using an active amino group-containing mono- or polyamide compound have an action of promoting dissociation of a blocked urethane prepolymer, and have poor storage stability, and polychlorination. It also promotes dehydrochlorination of vinyl and causes thermal yellowing. (B) When the blocking agent is an oxime, a lactam, or a phenol, the compatibility with vinyl chloride and a plasticizer is poor and the bleeding phenomenon occurs. However, there were problems such as the occurrence of such substances and the fact that the intended adhesive effect was not exhibited. (C) Further, phenols had problems such as odor.

[0006]

As described above, as long as the conventional technique is followed, it is excellent in long-term storage stability, and has good adhesion to various coated substrates, water resistance, chipping resistance, and discoloration resistance. It was difficult to provide a vinyl chloride resin composition capable of providing an excellent coating film in terms of properties and the like. Therefore, the problem to be solved by the present invention is to provide a vinyl chloride resin composition having excellent long-term storage stability and excellent coating film adhesion, water resistance, chipping resistance, and discoloration resistance. .

[0007]

Means for Solving the Problems The inventors of the present invention have focused their attention on the above-mentioned problems, and as a result of earnest studies,
As a vinyl chloride resin composition aimed at, by using a blocked polyisocyanate in which 0.357 equivalents or more are blocked with respect to 1 equivalent of an isocyanate group by a monoalcohol having a carbon number of 18 to 40 which is surprisingly inexpensive and easily available, It was found that a vinyl chloride resin composition excellent in adhesion, water resistance, chipping resistance and discoloration resistance can be obtained, and the present invention has been completed.

That is, according to the present invention, (A) a vinyl chloride polymer and / or a vinyl chloride copolymer, and (B) an isocyanate group of 0.357 equivalent or more per 1 equivalent of a carbon number 1.
The present invention relates to a vinyl chloride resin composition comprising an adhesion-imparting agent composed of a blocked polyisocyanate blocked with 8 to 40 monoalcohols and a plasticizer (C) as essential components.

The structure of the present invention will be described in more detail below. First, the vinyl chloride polymer and / or vinyl chloride copolymer (A) used in the present invention is a vinyl chloride homopolymer and / or vinyl chloride copolymer, and those which are commonly available can be used. .

That is, as the vinyl chloride copolymer, vinyl chloride and other vinyl monomers copolymerizable therewith, for example, vinyl acetate, maleic anhydride, esters thereof, vinyl ether and the like copolymers, Examples thereof include vinyl chloride-vinylidene chloride copolymer.

The degree of polymerization of these vinyl chloride polymers and / or vinyl chloride copolymers (A) is usually 700-4.
000, preferably 1000 to 2000. Commercially available vinyl chloride polymers or vinyl chloride copolymers are Kanevinyl PSL-10 and PSH-1.
0, PSM-30 and PCH-12 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.), ZEON 121 and 135J (manufactured by ZEON CORPORATION),
Denka Vinyl PA-100, ME-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.), Monsanto 70BK (manufactured by Mitsubishi Kasei Vinyl Co., Ltd.)
Is mentioned. Any of these can be used in the present invention, and two or more kinds of them can be mixed and used.

The plasticizer (C) used in the present invention is not particularly limited as long as it is a plasticizer which is liquid at ordinary temperature and used for a usual vinyl chloride polymer and / or vinyl chloride copolymer (A). Can be done. Specifically, for example, di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate (DOP), diisooctyl phthalate, octyldecyl phthalate, diisodecyl phthalate, butyl phthalate. Benzyl, di-isophthalate
Phthalates plasticizer such as 2-ethylhexyl, di-2-ethylhexyl adipate (DOA), di-n adipate
-Decyl, diisodecyl adipate, azelaic acid di-
Fatty acid ester-based plasticizers such as 2-ethylhexyl, dibutyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, tributyl phosphate, tri-phosphate
Phosphate ester plasticizers such as 2-ethylhexyl, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, epoxidized soybean oil, epoxidized tall oil fatty acid-2
-Epoxy plasticizers such as ethylhexyl and the like,
These 1 type (s) or 2 or more types are mixed and used.

The amount of the plasticizer (C) used is appropriately selected depending on the desired solid content concentration of the paste sol, the fluidity, the amount of the foaming agent used, the use of the foam, and the like. Generally, a vinyl chloride polymer and / or Or vinyl chloride copolymer (A) 100
30 to 400 parts by weight, preferably 50 to 2 parts by weight
It is used in the range of 00 parts by weight.

A part of the plasticizer (C) is a diluent such as texanol isobutyrate or dodecylbenzene,
Alternatively, it can be replaced with an organic solvent or the like for swelling the vinyl chloride polymer such as toluene or xylene and / or the vinyl chloride copolymer (A), and may be an organosol. The addition amount of these diluents and organic solvents is appropriately determined depending on the application.

0.35 per 1 equivalent of isocyanate group
The adhesion-imparting agent (B) consisting of a blocked polyisocyanate in which 7 equivalents or more is blocked with a monoalcohol having 18 to 40 carbon atoms is 0.3% per 1 equivalent of an isocyanate group containing an active isocyanate group-containing polyisocyanate.
Blocking and urethanization using a blocking agent having 57 equivalents or more of a monoalcohol having 18 to 40 carbon atoms in the absence of a solvent or in the presence of a solvent, a plasticizer, and / or a diluent. It can be prepared by soaking.

Of these, as the active isocyanate group (hereinafter referred to as active NCO group) -containing polyisocyanate, only typical ones will be exemplified.
Hexamethylene diisocyanate, 2,4-diisocyanate-1-methylcyclohexane, diisocyanate cyclobutane, tetramethylene diisocyanate,
o-, m- or p-xylylene diisocyanate,
Aliphatic or alicyclic diisocyanates, such as hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, lysine diisocyanate or isophorone diisocyanate,

Tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4,4'-diisocyanate, m- or p
-Phenylene diisocyanate, chlorophenylene-
2,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-1,3,5-triisopropylbenzene-2,4-diisocyanate, carbodiimide-modified diphenyl Various diisocyanates such as aromatic diisocyanates, such as metadiisocyanate or diphenyl ether diisocyanate,

Alternatively, an excess of various triisocyanates such as diphenylmethane triisocyanate is reacted with a polyhydroxy compound represented by various dihydric monoalcohols, trihydric monoalcohols or tetrahydric or higher polyhydric monoalcohols. The resulting polyurethane polyisocyanate, or a polyisocyanate containing an isocyanurate ring or a polyisocyanate containing an allophanate bond, which is obtained by polymerizing various diisocyanates or triisocyanates as listed above, and further reacts with water Examples thereof include polyisocyanates containing buret bonds.

Further, in the present invention, especially, JP-A-60-18 is used.
1114, at least one diisocyanate compound selected from the group consisting of alkylene diisocyanate, cycloalkylene diisocyanate and araalkylene diisocyanate, in the presence of an isocyanurate-forming catalyst selected from various isocyanate-forming catalysts described in the same publication. It is preferable to use an isocyanurate type polyisocyanate having an isocyanurate ring obtained by reacting.

As these polyisocyanates containing active NCO groups, aliphatic diisocyanates and alicyclic diisocyanates are particularly preferable from the viewpoints of discoloration and stability during baking.

These are alkylene diisocyanates,
One or more diisocyanate compounds selected from the group consisting of cycloalkylene diisocyanates and araalkylene diisocyanates, and having at least 3 or more hydrocarbon substituents in one molecule, having a molecular weight of 100 to 100.
It may be an isocyanurate ring-containing polyisocyanate obtained by reacting a diol of 0 with an isocyanurate-forming catalyst, and is selected from the group consisting of alkylene diisocyanates, cycloalkylene diisocyanates and alkylene diisocyanates. A polyisocyanate obtained by reacting an isocyanurate ring-containing polyisocyanate obtained from one or more diisocyanate compounds with a diol having at least 3 or more hydrocarbon substituents in one molecule and having a molecular weight of 100 to 1000. It may be.

The above-mentioned one molecule having 3 or more hydrocarbon substituents, which can be used in the present invention, has a molecular weight of 1
Examples of the polyol of 00 to 1000, that is, the polyhydroxy compound include 1,2,2-trimethyl-
1,3-propanediol (2,2-dimethyl-1,3
-Butanediol) or 2,2-dimethyl-3-isopropyl-1,3-propanediol (2,2,4-
Trimethyl-1,3-pentanediol) and the like, trimethylolpropane, glycerin, castor oil and the like are particularly representative, and further long-chain alkyl diol, polyether diol, polyester diol or polybutadiene glycol, etc. Alternatively, a mixture of two or more of these may be mentioned.

Examples of the long-chain alkyl diol mentioned here include propylene glycol, 1,4-butane diol, 1,6-hexane diol, 1,9-nonane diol, dodecane diol, 1,2-hydroxystearyl alcohol, Oleyl alcohol dimer, polybutadiene glycol and the like are particularly representative, and it is preferable to use a diol having 8 or more carbon atoms.

Examples of the polyether diol include polypropylene glycol, polytetramethylene glycol, polybutylene glycol and the like, and the use of polytetramethylene glycol is particularly preferable.

As the polyester diol, a polyester diol obtained by polycondensing a dicarboxylic acid and / or its anhydride or ester or acid halide with various diols as listed above is particularly representative. To be As the dicarboxylic acid,
Aliphatic dicarboxylic acids such as maleic acid, adipic acid, sebacic acid, dimer, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid, or alicyclic dicarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid and the like. The anhydrides are particularly representative.

Of these, particularly preferred are aliphatic dicarboxylic acids, and among them, aliphatic dicarboxylic acids having 4 or more carbon atoms are preferred. A polylactone polyol obtained by ring-opening polymerization of a lactone such as ε-caprolactone or γ-butyrolactone in the presence of the above-mentioned various diols can also be used. Examples of the above-mentioned polybutadiene glycol include compounds having a hydroxyl group at both ends of polybutadiene such as 1,2-type and 1,4-type, and "Polybutadiene glycol G-1000" (product of Nippon Soda Co., Ltd.) and the like. Commercially available products.

The blocking agent used in the present invention is a monoalcohol having 18 to 40 carbon atoms. 18 carbon atoms
A monoalcohol content of less than 1 is not preferable because a high dissociation temperature is required for use after blocking and the compatibility with the vinyl chloride polymer and / or the vinyl chloride copolymer (A) is poor. Further, monoalcohols having more than 40 carbon atoms have a drawback that they are usually difficult to obtain.

Therefore, the blocking agent used in the present invention is a long-chain primary, secondary or tertiary monoalcohol having 18 to 40 carbon atoms. When these primary, secondary or tertiary monoalcohols are used as a blocking agent, the dissociation temperature of the blocking group is generally higher as the carbon number of the monoalcohol is smaller, and the primary>secondary> tertiary. The use of higher monoalcohols is particularly preferable when considering the problem of odor and low-temperature dissociation property, because monoalcohols increase in order.

The odor problem is that if the carbon number of the monoalcohol used is 18 or more (n-octanol or more),
Usually no problem.

Typical examples of these are octadecyl alcohol, hexacosyl alcohol, melysyl alcohol, Hysocol 246 (a mixture of saturated primary alcohols having a side chain structure of 24 to 26 carbon atoms, Ito Oil Co., Ltd.). (Manufactured by the company) or the like, or oleyl alcohol or the like as the unsaturated monoalcohol. Furthermore, the carbon number is 18-
Alicyclic monoalcohols of 40 can be used in the present invention as well.

Other blocking agents used for blocking include malonic acid diesters (diethyl malonate, etc.), acetoacetic acid esters (ethyl acetoacetate, etc.), acetylacetone, etc. as active methylene compounds. As a compound, acetoxime, ketoxime (for example, methylethylketoxime (butanone oxime)), as a phenol compound, phenol, cresol, etc., as a lactam compound, ε-caprolactam, etc.,
2-Methylimidazole and the like are known as imidazole compounds, and N-ethylacetamide, N-phenylacetamide and the like are known as monoamide compounds.
(JP-A-57-145161)

One or more of these blocking agents may be mixed with a monoalcohol having 18 to 40 carbon atoms and used in an amount of 0.357 equivalent based on 1 equivalent of the isocyanate group in the polyisocyanate. 18 to 4 carbon atoms
Block with 0 monoalcohol. The addition amount of the blocking agent is 1 equivalent or more and less than 1.5 equivalents based on the equivalent of the isocyanate group in the polyisocyanate,
It is preferably in the range of 1.0 to 1.2 equivalents. The blocking reaction temperature is usually 40 to 140 ° C., and it is preferable to add a known urethanization catalyst such as an organic tin compound, a tertiary amine, and a metal alcoholate during the reaction to accelerate the reaction.

The reaction can be carried out without a solvent, but it is preferable to carry out the reaction in a solvent and / or a diluent in view of workability at the time of taking out. As these solvents and diluents, an extremely wide range can be used. Typical examples are the plasticizers, acetic acid esters, (ethyl acetate, butyl acetate, etc.), ketones, ethers, aromatic compounds mentioned above. Examples include solvents.

The blocked polyisocyanate obtained as described above usually has a molecular weight of 500 to 5,000, preferably 600 to 3,000. When the molecular weight is less than 600, when it is used for a vinyl chloride sol, it becomes hard and brittle and its physical properties deteriorate. On the other hand, when it exceeds 5,000, the adhesion to the substrate is lowered, which is not preferable. Further, the vinyl chloride resin composition of the present invention may contain various other additives such as stabilizers and fillers, lubricants, pigments, dissociation accelerators, and diluents within a range that does not impair the object of the present invention. it can.

As the stabilizer, metal soaps (calcium stearate, zinc stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphite, dibasic sulfate, etc.), organometallic compounds (organic Dibutyl tin malate, dioctyl tin malate as tin stabilizer,
Dioctyl tin bis (2-ethylhexyl malate, etc.)
Examples include epoxidized soybean oil.

As the filler, inorganic fillers (hydrous silicic acid, calcium carbonate, talc, diatomaceous earth, kaolin clay, barium sulfate precipitated, etc.) and organic fillers (cellulose, polyethylene terephthalate, acrylic, etc.) Examples thereof include thermoplastic resins such as rubber-based and urethane-based resins.

As the lubricant, in addition to metal soaps,
There are various paraffins, waxes, fatty acid esters, fluorohydrocarbons, organic silicons, etc. The pigment may be any pigment used for the purpose of merely coloring, and various pigments (for example, titanium oxide, minerals such as red iron oxide) Pigments and organic pigments such as carbon black and phthalocyanine blue) are used alone or in combination.

[0038] For the purpose of accelerating the reaction of the vinyl chloride resin composition at the time of heating to lower the heat treatment temperature in practical use and shortening the reaction time, dissociation of the blocked urethane prepolymer is promoted. Usually used catalysts for, for example, zinc octylate, tin octylate, dibutyltin dilaurate, organometallic compounds such as dibutyltin acetate, tritriethylenediamine, triethylamine, 1,8-diazacycloundecene-7 salt, and the like,
It is also preferable to use a quaternary ammonium salt or the like as a dissociation accelerator in combination with the composition of the present invention.

As a diluent, the boiling point is 70 to 240 ° C.
(1 atm) aliphatic solvent (C6 or more paraphene hydrocarbon solvent such as hexane, heptane, octane, nonane, decane), naphthene hydrocarbon solvent (cyclohexane, methylcyclohexane, dimethylcyclohexane, diethylcyclohexane, trimethyl) Cyclohexane, etc.), and mixed solvents of the above solvents, aromatic solvents (for example, toluene, xylene, ethylbenzene, styrene,
Solvesso # 100 [manufactured by Esso Kagaku Co., Ltd.] Solvesso # 150 [manufactured by Esso Kagaku Co., Ltd.] and the like can also be used, and mineral spirits (for example, Rousse, which is a mixed system of an aliphatic solvent and an aromatic solvent). House [made by Shell Chemical Co., Ltd.]) can also be used. Furthermore, as a part of the solvent component, the boiling point is extremely high, for example, liquid high-boiling point aromatic hydrocarbon compounds SAS-296, SAS-LH.
(Manufactured by Nippon Petrochemical Co., Ltd.) and dimer acid can also be used.

In the vinyl chloride resin composition of the present invention, the compounding ratios of the respective components (A), (B) and (C) are as shown in Table 1. (Here,% is% by weight.)

[0041]

[Table 1]

In the present invention, when a stabilizer is used as an additive, it is usually 0 to 5% by weight (preferably 0.1% by weight).
.About.3% by weight), usually 0 to 7% by weight (preferably 1 to 5% by weight) when a diluent is used, and usually 0 to 1% by weight (preferably 0) when a dissociation promoter is used. ~ 0.3
% By weight) is used. The vinyl chloride resin composition of the present invention having such a composition can be produced by kneading by a conventional method.

The vinyl chloride resin composition of the present invention can be applied to various metal substrates and various coated surfaces applied to metal (especially steel) surfaces, but in particular, cationic electrodeposition coated surfaces and acrylic resin coated surfaces. , Can be advantageously applied to metal surfaces. Cationic electrodeposition coating is, for example, a polyamine resin, that is, a blocked isocyanate that reacts with an amino group or a hydroxyl group in the molecule is used as a film-forming component, and this is neutralized with a lower organic acid or the like to give an aqueous solution or aqueous dispersion. This is a coating method in which a film-forming component is present as cations when a coating material is used, and the coating material (such as a steel plate) is used as a cathode to deposit the coating material on the surface of the coating material by direct current application.

As the acrylic resin paint used for the acrylic resin coating, there are thermoplastic type and thermosetting type. The thermoplastic type is an acrylic (co) polymer mainly used for room temperature drying in combination with a fibrin derivative (nitrified cotton, cellulose acetate butyrate, etc.), a plasticizer and the like. The thermosetting type has a functional group in an acrylic (co) polymer and is capable of being crosslinked by itself or by a reaction with a crosslinking agent to form a coating film.

The coating amount of the vinyl chloride resin composition of the present invention on the above coated surface is usually 150 to 3000 g / m ^2.
The coating thickness is usually 0.15 to 3 mm. Further, after application, baking is carried out. In that case, the baking temperature is usually 110 to 150 ° C., and the baking time is usually 20 to
40 minutes. As a coating method, a usual method such as spray coating, brush coating, dipping, pouring, pouring, airless spraying or the like can be used. As a general coating method of the vinyl chloride resin composition of the present invention, electrostatic coating, sticky coating and the like can be mentioned in addition to those described above.

The vinyl chloride resin composition of the present invention can be applied to many substrates such as cationic electrodeposition coated surface, acrylic coated surface,
Baking at low temperature for a short time on a metal surface (120 to 130
It adheres firmly at (° C x 20 to 30 minutes) and does not discolor. At the same time, it is far more stable than the conventional one, and shows little increase in viscosity even under severe conditions of 45 ° C./10 days. Further, the vinyl chloride resin composition of the present invention is excellent in chipping resistance, baking type paint, adhesive,
It can be applied to various industrial applications such as sealant and caulk, but it is especially excellent for automobiles, especially undercoating with various coatings, or as a body sealer or undercoat for vehicle bodies.

[0047]

EXAMPLES The present invention will be described in more detail with reference to examples, comparative examples and application examples, but the present invention is not limited to these. In the examples, "part",
"%" Is based on weight unless otherwise specified.

(Synthesis Example 1) (Synthesis of isocyanurate type polyisocyanate of hexamethylene diisocyanate) Nitrogen gas atmosphere in a 4-liter glass four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, an air cooling tube and a thermometer. Hexamethylene diisocyanate (abbreviation HDI, molecular weight 1
68.2) Charge 1400 g. After heating with an oil bath, the temperature was raised to 55 ° C. under stirring, and the mixture was kept for 1 hour, and then a 16% concentration butyl cellosolve solution of β-methylcholine octoate (abbreviation CO, molecular weight 261.4) was used as an isocyanurate-forming catalyst. 3.9 g (2.39 mmol) was added and reacted.

An exotherm was observed as the reaction started, and the temperature in the reactor rose to 62 ° C. After the exotherm subsided, the temperature in the reactor was kept at 60 ° C., and after the reaction was continued for a total of 4.5 hours, xylene having a concentration of 5.8% of monochloroacetic acid (molecular weight 94.5) was used as a catalyst deactivator. Solution 3.9
The reaction was terminated by adding g (2.39 mmol) into the reactor. After cooling the reaction mixture to room temperature, the reaction mixture 100
0 g was subjected to molecular distillation to obtain polyisocyanate (1) 33
8g (conversion rate 33.8%) and effluent 662g (recovery rate 6
6.2%).

The obtained polyisocyanate (1) is a liquid substance which has fluidity at room temperature, and when diluted to a non-volatile content of 75.0% with ethyl acetate, the Gardner viscosity A _2-
A ₁ , the isocyanate content was 16.4%, and it was confirmed to contain an isocyanurate ring, and its average molecular weight was 6
It was 19. On the other hand, analysis of the effluent during molecular distillation confirmed that this was essentially pure HDI.

(Synthesis Example 2) [Synthesis of 1,3-bis (isocyanatomethyl) -cyclohexane (abbreviation H ₆ XDI, molecular weight 194.2) isocyanurate type polyisocyanate] In the same manner as in Synthesis Example 1, 1 , 3-bis (isocyanatomethyl) -cyclohexane 1400 g was used as a catalyst for isocyanurate, and a reaction was carried out using 5.5 g (3.37 mmol) of a 16% concentration CO butyl cellosolve solution. After a predetermined reaction time, 5.5 g (3.3%) of a 5.8% xylene solution of monochloroacetic acid as a catalyst deactivator.
7 mmol) was converted to terminate the reaction, and polyisocyanate (2) was obtained in the same manner as in Synthesis Example 1.

The conversion rate of this reaction was 37.8%, and the polyisocyanate (2) obtained had the following properties and analysis results: when diluted with ethyl acetate to a nonvolatile content of 75%, the number of colors was 1.
Hereafter, the Gardner viscosity was I ² -J, the isocyanate content was 14.9%, and the average molecular weight was 637. As a result of analysis of the effluent during molecular distillation, this product was almost pure H ₆ XDI.

(Synthesis Example 3) [2,2,4-methyl-1,
3-Pentanediol (abbreviation TMPD, molecular weight 146.
2) Synthesis of Isocyanurate-Type Polyisocyanate of Modified HDI] By the same method as in Synthesis Example 1, 1400 g of HDI was obtained.
(8.32 mol), TMPD 50 g (0.34 mol)
Charge. The temperature was raised to 55 ° C. with stirring, and after holding for 1 hour, a 16% CO butyl cellosolve solution as an isocyanurate-forming catalyst was dividedly added to the reactor, and the total catalyst solution was 2.4 g (1.47 mmol). ) At the time of addition, the reaction started and an exotherm was observed, and the temperature in the reactor rose to 62 ° C.

After the exotherm subsided, the temperature in the reactor was raised to 6
After keeping at 0 ° C. and reacting for a total of 4.5 hours, monochloroacetic acid (molecular weight 94.
2.4 g of a 5.8% strength xylene solution of 5) (1.47 m
mol) was added to the reactor to terminate the reaction. After cooling the reaction mixture to room temperature, 1000 g of the reaction mixture was subjected to molecular distillation to obtain 331.3 g of polyisocyanate (3) (conversion rate 33.1%).

The polyisocyanate (3) thus obtained is a liquid substance having fluidity at room temperature, and when diluted with ethyl acetate at 75%, the Gardner color number is 1 or less and the Gardner viscosity is A.
_1- A, the isocyanate content was 15.0%, the result of analysis was confirmed to contain an isocyanurate ring, and the average molecular weight was 654. On the other hand, analysis of the effluent of molecular distillation confirmed that this was essentially pure HDI.

(Synthesis Example 4) By the same method as in Synthesis Example 1, 841 g of HDI (5.
0 mol) and 134 g (1.0 mol) of trimethylolpropane (abbreviation TMP, molecular weight: 134) are charged. The flask is placed in an oil bath, the temperature is raised to 60 ° C. with stirring, and the temperature inside the reactor is maintained at 60 ° C. After the exotherm has subsided, the temperature inside the reactor is maintained at 60 ° C. and the reaction is continued for 5 hours.
After the reaction mixture was cooled to room temperature, 1000 g of the reaction mixture was subjected to molecular distillation to obtain 638.6 g of polyisocyanate (4).
Got

The obtained polyisocyanate (4) is a liquid substance which has fluidity at room temperature, and is 75% with ethyl acetate.
When diluted by%, the Gardner color number was 1 or less, the Gardner viscosity was JK, and the isocyanate content was 12.8%.

(Synthesis Example 5) Vernock D-802 (manufactured by Dainippon Ink and Chemicals, Inc .: polymer of tolylene diisocyanate, nonvolatile content 50%, Gardner viscosity U to X, effective isocyanate content 7.5%) The solvent was butyl acetate), and polyisocyanate (5) was obtained in the same manner as in Synthesis Example 1.

(Production Examples 1 to 7) (Synthesis of Block Polyisocyanate) A 2-liter four-necked flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a Liebig cooling tube was attached according to Tables 2 and 3.
Polyisocyanate (1) obtained in Synthesis Examples 1 to 5
(5), dioctyl phthalate serving as a blocking agent and a diluent was charged and reacted at 80 ° C. for 1 hour while stirring. Then, a blocking agent was gradually added according to Tables 2 and 3, and the mixture was reacted at 90 ° C for about 1 hour. The absorption rate of the isocyanate group (2250 cm ⁻¹ ) disappears completely according to the infrared absorption spectrum, so that the isocyanate content is 0.
Was confirmed.

When the blocking reaction was incomplete in about 1 hour, a small amount of the blocking agent was added, and the reaction was further continued to complete the blocking. Thus, dioctyl phthalate solutions (i) to (vii) of blocked polyisocyanate which are soluble in a liquid plasticizer at room temperature were obtained.

(Examples 1 to 5) and (Comparative Examples 1 to 3) Vinyl chloride resin compositions (plastisol compositions) were prepared as follows. Kanevinyl PSL-10 (Kanefuchi Chemical Industry Co., Ltd., vinyl chloride straight resin) 7
0 parts, Kanevinyl PCH-12 (Kanefuchi Chemical Co., Ltd., vinyl chloride copolymer resin) 30 parts, dioctyl phthalate (DOP) 100 parts, NS # 100 (Nitto Koka Kogyo Co., Ltd. calcium carbonate) 100 parts , And a vinyl chloride paste consisting of 3 parts of dibasic lead phosphite (daiphos) (303 parts in total) and dioctyl phthalate solutions (i) to (vii) of block polyisocyanate were uniformly mixed in a kneading machine according to Tables 4 to 5. Was kneaded to prepare vinyl chloride resin compositions, which were referred to as Examples 1 to 5 and Comparative Examples 1 and 2. Further, as Comparative Example 3, a vinyl chloride resin composition containing no blocked polyisocyanate was prepared.

The following tests were conducted using the vinyl chloride resin compositions obtained in Examples 1-5 and Comparative Examples 1-3. (1) A change in viscosity when stored at a predetermined temperature was tested. (2) Steel sheet coated with cationic electrodeposition coating (cation ED
The obtained vinyl chloride resin composition was applied to a board so that the coating film thickness would be 0.25 mm, and baked at 140 ° C. for 20 minutes to test the discoloration resistance.

(3) Adhesion of the vinyl chloride resin composition to the base material on the cation electrodeposition plate is determined by a method of flattening (JA
S, special plywood standard), and measured with a universal tensile tester. (4) The chipping resistance is tested by a nut drop test (nut No.
Using M-4, a nut is dropped from a height of 2 m on a coating film with an angle of 60 degrees, and the chipping resistance is measured from the weight of the nut required until the film is broken. ) Was measured.

The above results are shown in Tables 4 to 5, and it can be seen that the examples are superior to the comparative examples in stability, adhesion and discoloration resistance.

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4] (Note) * Thickness increase rate: Viscosity V ₂ after acceleration of heating to initial viscosity V ₁
Was subtracted and divided by the initial viscosity to obtain%.

[0068]

[Table 5] (Note) * Thickness increase rate: Viscosity V ₂ after acceleration of heating to initial viscosity V ₁
Was subtracted and divided by the initial viscosity to obtain%.

[0069]

INDUSTRIAL APPLICABILITY The present invention has excellent long-term storage stability, excellent adhesion to various substrates, and discoloration resistance.
It is possible to provide a vinyl chloride resin composition which forms a coating film having excellent chipping resistance and is particularly useful as a coating material for automobiles and a sealing agent.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09D 5/00 C09D 5/00 C09K 3/10 C09K 3/10 (56) Reference JP-A-6-16769 (JP, A) JP-A-2-296851 (JP, A) JP-A-62-190267 (JP, A) JP-A-62-256852 (JP, A) JP-A-63-10615 (JP, A) JP-A-62-41278 (JP, A) JP-A-57-105441 (JP, A) JP-A-1-170633 (JP, A) JP-A-2-255853 (JP, A) JP-A-2-163146 (JP, A) (JP-A) 58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 27/06 C08G 18/62 C08G 18/80 C08L 75/04-75/16 C09D 5/00-5/46

Claims (2)

(57) [Claims] 1. A vinyl chloride polymer and / or a vinyl chloride copolymer (A) and 1 equivalent of an isocyanate group (B).
A vinyl chloride resin composition comprising, as essential components, an adhesion-imparting agent consisting of a blocked polyisocyanate in which 0.357 equivalent or more is blocked with a monoalcohol having 18 to 40 carbon atoms , and (C) a plasticizer. . Wherein the polyisocyanate in the adhesive imparting agent comprising the blocked polyisocyanate contains configured isocyanurate rings from one or more diisocyanates selected from the group consisting of alkylene diisocyanates, cycloalkylene diisocyanates and aralkylene diisocyanate The resin composition according to claim 1, which is a polyisocyanate.